Deuterium Nuclear Magnetic Resonance is used to probe anisotropic molecular motion in oriented liquid crystals and fibrous proteins. Quadrupolar splittings of small molecules solvating polypeptides and splittings from specifically labeled polymers yield the degree of orientational order. New insights of local motions are derived from fitting models of molecular dynamics to the experimental observations. The investigations are carried out on polymeric liquid crystals, uniaxial strained synthetic elastomers, and oriented fibrous proteins such as collagen.